EP0549593B1 - Procede de racemisation d'acides 3-oxocyclopentancarboxyliques ou hexancarboxyliques non racemiques ou de leurs esters avec des alcools c 1-c 6 - Google Patents

Procede de racemisation d'acides 3-oxocyclopentancarboxyliques ou hexancarboxyliques non racemiques ou de leurs esters avec des alcools c 1-c 6 Download PDF

Info

Publication number
EP0549593B1
EP0549593B1 EP91913842A EP91913842A EP0549593B1 EP 0549593 B1 EP0549593 B1 EP 0549593B1 EP 91913842 A EP91913842 A EP 91913842A EP 91913842 A EP91913842 A EP 91913842A EP 0549593 B1 EP0549593 B1 EP 0549593B1
Authority
EP
European Patent Office
Prior art keywords
racemic
esters
racemization
alcohol
acids
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91913842A
Other languages
German (de)
English (en)
Other versions
EP0549593A1 (fr
Inventor
Rainer Sobotta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boehringer Ingelheim International GmbH
Boehringer Ingelheim GmbH
Original Assignee
Boehringer Ingelheim International GmbH
Boehringer Ingelheim GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boehringer Ingelheim International GmbH, Boehringer Ingelheim GmbH filed Critical Boehringer Ingelheim International GmbH
Publication of EP0549593A1 publication Critical patent/EP0549593A1/fr
Application granted granted Critical
Publication of EP0549593B1 publication Critical patent/EP0549593B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C62/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C62/18—Saturated compounds containing keto groups
    • C07C62/24—Saturated compounds containing keto groups the keto group being part of a ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification

Definitions

  • the invention relates to a new process with which non-racemic 3-oxocyclopentane or 3-oxocyclohexane carboxylic acid or its esters can be racemized with lower alcohols to give the corresponding racemic acids or esters.
  • the invention now solves the problem of converting enantiomers or non-racemic enantiomer mixtures of 3-oxocycloalkanecarboxylic acids or their esters with lower alcohols into the racemate.
  • Racemization is not possible using customary methods, for example by the action of bases on non-racemic 3-oxocycloalkane carboxylic acids or their esters; it there are predominantly condensation products.
  • the process is characterized in that the acids or esters are ketalized with a C 1 -C 6 -alkyl orthoformate in the presence of catalytic amounts of a strong acid in a C 1 -C 6 alcohol as the reaction medium and (if not already a Ester is present) esterified at the same time, the product obtained is racemized by the action of an alcoholate, then hydrolyzed by treatment with dilute acid to give the racemic acid or racemic ester and the racemic compounds are isolated in a conventional manner.
  • the sub-steps are expediently carried out without isolating intermediate products.
  • the alcohol used is an aliphatic alcohol with 1-6 carbon atoms, preferably methanol, ethanol, propanol. It is advisable to use orthoformic acids and alcoholates (e.g. sodium or potassium alcoholates), which are derived from the same alcohol that serves as the reaction medium.
  • the acids used for these purposes strong mineral acids such as sulfuric acid, hydrochloric acid; toluenesulfonic acid, methanesulfonic acid) are used as catalysts.
  • the ketal is preferably prepared at the boiling point of the reaction mixture.
  • the hydrolysis the ketal function (to the ester) is carried out at room temperature or with cooling. If the ester group is also to be hydrolyzed, this is expediently carried out at the reflux temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (5)

  1. Procédé pour racémiser des acides 3-oxocyclopentane- ou -hexanecarboxyliques non racémiques ou leurs esters avec des alcools en C1-C6, caractérisé en ce que l'on cétalise ces acides ou esters avec un orthoformiate d'alkyle en C1-C6 en présence de quantités catalytiques d'un acide fort dans un alcool en C1-C6 comme milieu réactionnel et (si un ester n'est pas déjà présent) on les estérifie en même temps, on racémise le produit obtenu par action d'un alcoolate, puis on l'hydrolyse en l'acide racémique ou en l'ester racémique par traitement avec un acide dilué et on isole les composés racémiques de manière habituelle.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise pour la racémisation un alcoolate de sodium ou de potassium.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'un alcool en C1-C3 est utilisé comme milieu réactionnel et l'orthoester et l'alcoolate dérivent du même alcool.
  4. Procédé selon la revendication 3, caractérisé en ce que l'alcool est le méthanol ou l'éthanol.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que l'hydrolyse pour l'obtention des acides racémiques a lieu à la température d'ébullition, l'hydrolyse pour l'obtention des esters racémiques a lieu à la température ambiante ou sous léger refroidissement.
EP91913842A 1990-08-04 1991-07-31 Procede de racemisation d'acides 3-oxocyclopentancarboxyliques ou hexancarboxyliques non racemiques ou de leurs esters avec des alcools c 1-c 6 Expired - Lifetime EP0549593B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4024836 1990-08-04
DE4024836A DE4024836A1 (de) 1990-08-04 1990-08-04 Verfahren zur racemisierung
PCT/EP1991/001434 WO1992002483A1 (fr) 1990-08-04 1991-07-31 Procede de racemisation d'acides 3-oxocyclopentancarboxyliques ou hexancarboxyliques non racemiques ou de leurs esters avec des alcools c1-c¿6?

Publications (2)

Publication Number Publication Date
EP0549593A1 EP0549593A1 (fr) 1993-07-07
EP0549593B1 true EP0549593B1 (fr) 1996-10-09

Family

ID=6411682

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91913842A Expired - Lifetime EP0549593B1 (fr) 1990-08-04 1991-07-31 Procede de racemisation d'acides 3-oxocyclopentancarboxyliques ou hexancarboxyliques non racemiques ou de leurs esters avec des alcools c 1-c 6

Country Status (18)

Country Link
US (1) US5488136A (fr)
EP (1) EP0549593B1 (fr)
JP (1) JP3032987B2 (fr)
KR (1) KR100190773B1 (fr)
AT (1) ATE143937T1 (fr)
AU (1) AU645595B2 (fr)
CA (1) CA2088774C (fr)
CZ (1) CZ281079B6 (fr)
DE (2) DE4024836A1 (fr)
DK (1) DK0549593T3 (fr)
ES (1) ES2094817T3 (fr)
GR (1) GR3021370T3 (fr)
HU (1) HU212610B (fr)
NO (1) NO177422C (fr)
PL (1) PL166566B1 (fr)
RU (1) RU2058281C1 (fr)
SK (1) SK280699B6 (fr)
WO (1) WO1992002483A1 (fr)

Also Published As

Publication number Publication date
HUT64291A (en) 1993-12-28
GR3021370T3 (en) 1997-01-31
HU212610B (en) 1996-09-30
SK5193A3 (en) 1993-11-10
DE4024836A1 (de) 1992-02-06
CA2088774A1 (fr) 1992-02-05
AU8291591A (en) 1992-03-02
CZ12693A3 (en) 1994-01-19
AU645595B2 (en) 1994-01-20
KR930701379A (ko) 1993-06-11
WO1992002483A1 (fr) 1992-02-20
DE59108272D1 (de) 1996-11-14
NO177422C (no) 1995-09-13
JP3032987B2 (ja) 2000-04-17
ATE143937T1 (de) 1996-10-15
NO177422B (no) 1995-06-06
ES2094817T3 (es) 1997-02-01
HU9300287D0 (en) 1993-05-28
SK280699B6 (sk) 2000-06-12
KR100190773B1 (ko) 1999-06-01
CA2088774C (fr) 2004-02-10
CZ281079B6 (cs) 1996-06-12
US5488136A (en) 1996-01-30
DE4024836C2 (fr) 1992-07-02
RU2058281C1 (ru) 1996-04-20
EP0549593A1 (fr) 1993-07-07
DK0549593T3 (da) 1996-11-18
NO930383D0 (no) 1993-02-03
JPH06502393A (ja) 1994-03-17
PL166566B1 (pl) 1995-06-30
NO930383L (no) 1993-02-03

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